Process for breaking petroleum emulsions



Patented Oct. 27, 1942 PROCESS FOR BREAKING PETROLEUM EMULSIONS Edwin E.Clayton, Long Be Petrolite Corporation, Ltd.,

ach, CaliL, amignor to Wilmington, DeL,

a corporation of Delaware No Drawing. Application June 19, 1941, SerialNo. 398,814

8 Claims.

This invention relates to the resolution of petroleum emulsions.

The main object of my invention is to provide a novel process forresolving petroleum emulsions of the water-in-oil type that are commonlyreferred to as cut oil, roily oil, emulsified oil, etc., and whichcomprise fine droplets of naturally-occurring waters or brines dispersedin a more or less permanent state throughout the oil which constitutesthe continuous phase of the emulsion.

Another object of my invention is to provide an economical and rapidprocess for separating emulsions which have been prepared undercontrolled conditions from mineral oil, such as crude oil and relativelysoft waters or weak brines. Controlled emulsification and subsequentdemulsification under the conditions just mentioned is of significantvalue in removing impurities, particularly inorganic salts from pipeline oil.

In my improved process, hereinafter described in detail, derivatives ofthe water-soluble type of petroleum acid, commonly known as green acidor acids, are used as a demulsifier to resolve or break a petroleumemulsion of the water-inoil type.

Petroleum sulfonic acids,are produced from a Wide variety of petroleumdistillates or petroleum fractions, and in some instances they areproduced from the crude petroleum itself. When produced from crudepetroleum itself it is customary to use crude oil of the naphthenictype, crude oil of the paraffin type, crude oil of the asphaltic typeand mixtures of said three different types of crude oil.

The art of refining crude petroleum or various fractions, using sulfuricacid of various strengths, as well as monohydrate and fuming acid, is awell known procedure. In such conventional refining procedure, petroleumsulfonic acids have been produced asby-products. For instance, inremoving the olefinic components, it has been common practice to usesulfuric acid so as to polymerize the olefines or convert them intosulfonic acids which are subsequently removed. Likewise, in theproduction of white oil, or highly refined lubricating 0115, it has beencustomary to treat with fuming sulfuric acid, so as to eliminate certainundesirable components.

In recent years, certain mineral oil fractions have been treated withsulfuric acid with the primary object of producing petroleum sulfonicwill be herein referred to as water-soluble, without any efiort toindicate whether the solution is molecular or colloidalin nature. Thegreen acids, as indicated by their name, frequently give an aqueoussolution having a dark green or graygreen appearance. They generallyappear as a component of the acid draw-off, and do not remain behinddissolved in the oil fraction which has been subjected to sulfuric acidtreatment. The green acids are not soluble in oil, even whensubstantially anhydrous, and certainly are not soluble in oil when theycontain as much as 15% of water. Similarly, their salts obtained byneutralizing the green acids with a strong solution of caustic sode,caustic potash, or ammonia, are not oil-soluble. For convenience ofclassification, the ammonium salt will be considered as an alkali salt.

In contradistinction to the hydrophile green acids, there occurs as inthe manufacture of medicinal white oil, the oil-soluble type or themahogany acids. These mahogany acids are characterized by being solublein oil, especially acids, and in such procedure the petroleum sulfonicacids represented the primary products of reaction, rather thanconcomitant by-products.

when anhydrous, and being soluble in oil, even if they contain somedissolved water. Some of the mahogany acids also show limitedhydrophilic properties to the extent that either some water can bedissolved in the acids, or they, in turn, may dissolve to some extent inwater. In some instances their salts, such as the sodium, ammonium, orpotassium salt, will dissolve in water to give a colloidal sol. However,regardless of the presence of any hydrophilic properties whatsoever,they always have a characteristic hydrophobe property, as indicated bythe fact that the substantially anhydrous form, for instance, theiralkali salts containing 512% water, will dissolve in oil. This clearlydistinguishes them from the green acids previously referred to, becausethe green acids in similar form containing the same amount of water, forexample, will not dissolve in oil. The green acids, as such, areessentially hydrophilic and non-hydrophobic in character.

The utility of the mahogany acids in various arts has been enhanced byincreasing their water-solubility; for instance, converting the ,ma-

hogany acids into hydroxy alkylamine salts. On the other hand, as far asI am aware, no valuable product of commerce has resulted from decreasingthe water solubility of the mahogany acids by the addition of someoil-soluble basic amine, such as, for example, triamylamine. Thetriamylamine salts of mahogany acids, for example, are completely devoidof any solubility in water which the alkali salts may have exhibited andshow, as would be expected, an increased solubility in hydrophobesolvents.

Green acids are hydrophile in character, as previously stated. Theirhydrophile character has been increased by neutralization with materialssuch as triethanolamine and the like. Such green acid salts, havingenhanced water solubility, as compared with the ordinary alkali salts,havefound application incertain arts.

I have found that if green acids, of the oilinsoluble type, areneutralized with a heat-polymerized basic hydroxyamine of the kindhereinafter described, the resultant product has pronounced value as ademulsifier for oil field emulsions of the water-in-oil type, eitherwhen used alone, or when used in conjunction with other compatible andwell-known demulsifiers. Heatpolymerized basic hydroxyamines are wellknown compounds and are described in detail, for example, in U. S.Patent No. 2,231,758, dated February 11, 1941, to De Groote, Keiser andBlair. For purposes of convenience, the subsequent description of suchheat-polymerized basic hydroxyamines is substantially identical withthat found in the aforementioned U. S. Patent No. 2,231,758.

It is well known that alkylol amines or similar basic hydroxy amines, i.e., amines characterized by the fact that there is no aryl radicaldirectly attached to the amino nitrogen atom, can be polymerized byheating to elevated temperature, particularly in the presence ,ofsuitable catalysts. Generally speaking the catalysts are basicmaterials, or materials having a basic reaction, such as caustic soda,soap and the like. Polymerized amines contain two or more amino nitrogenatoms, but the most desirable form for my purpose is the form in whichthere are at least three nitrogen atoms present, and not more than fivenitrogen atoms. Such amines may be polymer.- ized to the degree that thematerial shows surface activity, when dissolved in water, either in theform of the amine (forming a base with water, of course), or in the formof a salt, such as the acetate. For the sake of convenience, I willrefer to the polymerized amines, broadly, as the polymerized product. Iwill refer to. the form containing two nitrogen atoms as thedimericform, and the type containing three, four or five nitrogen atoms, as thepolymeric form. When sufficiently polymerized, the product will besurface active. This means that a dilute solution, as such, or in theform of the acetate (for instance, one tenth of 1% to 1%) will foam. Iwill refer to such type as the highly polymerized surface active form.In actual practice, the amine that is available mostcheaply and which poymerizes most readily and which gives the most desirable type ofdemulsifier, is triethanolamine, particularly commercialtriethanolamine, which, as is known, contains a smallamount ofmonoethanolamine and an appreciable amount of diethanolamine. Thecomposition of such polymerized amines is not definitely known, exceptthat the polymerization takes place obviously by virtue of etherlinkages. Examination of triethanolamine, for example, indicates thatcyclic polymers could be formed or linear polymers could be formed, orpolymers could be formed which involve both linear and cyclicformations.

Needlessto say, since polymerization involves ether linkages, one mayinclude a polyhydric alcohol, such as a glycol or glycerol, recinoleylalcohol, or one might include polyhydric alcohols containing etherinkages, such as diethylene glycol, diglycerol, triglycerol,tetraglycerol, and the like. Monohydric alcohols, of course, can beemployed only to form ether linkages with a terminal hydroxyl group.Thus, one mole of triethanolamine, for example, and three moles of ethylalcohol might not form a highly polymerized material. is readilyunderstood, in view of the common theory of polyfunctionality in regardto resinous or subresinous materials derived from polyhydric alcoholsand polybasic acids. 'To produce highly polymerized materials one musthave retactants which are at least bifunctional. In polymerizations ofthe kind described the polyhydroxylated amines are bifunctional orpolyfunctional intermolecularly. Monohydroxylated amines, such asethanolamine, or a diethylethanolamine, are in the same class asmonohydric alcohols, i. e., they are monofunctional, unless, as far asthe material such as monoethanolamine is concerned, the hydrogen atomsattached to amino nitrogen atom could be removed with the formation ofwater, with the result that instead of an ether linkage, there is adirect carbon atom, nitogen atom bond. Thus, in the claims referencewill be made to the polymerization of polyfunctional alkylol amines,

the intention being to emphasize this particular feature. As has beenindicated, however, monofunctional compounds, such as monohydricalcohols, and certain monohydroxy amines are acceptable to form part ofthe polymerized compound or composition. Furthermore, polyhydricalcohols may be employed to produce the same polymeric structures aspolyhydrated amines. The preferred type of compound, however, isprepared without the introduction of polyhydric alcohols, such asglycerols, glycols, and the like. If desired, such particular type ofpreferred polymer may be indicated as being free from polyhydric alcoholresidues, or more broadly, free from alcohol residues, the word alcoholbeing used in the sense to refer to non-amino bodies, 1. e., the glycolsand glycerols, and is not intended to refer to aminoalcohols as the termis sometimes used in the description of triethanolamine or the like.

The polymerization of the basic hydroxy amines is effected by heatingsame at elevated temperatures, generally in the neighborhood of 200 to270 C., preferably, in the presence of catalysts, such as sodiumhydroxide, potassium hydroxide, sodium ethylate, sodium glycerate, orcatalysts of the kind commonly employed in the manufacture ofsuperglycerinated fats and the like. The proportion of catalystsemployed may vary from slightly less than one tenth of 1% in someinstances, to slightly over 1% in other instances.-

Needless to say, in the event the alcohol amine is low boiling,customary precautions must be taken so as not to lose part of thereactants. On the other hand, conditions must be such as to permit theremoval of water formed during the process. At times the process can beconducted most readily by permitting part of the volatile constituentsto distill, and subsequently subject- Theprinciple involved, of course,

the xylene. The dried condensate is then returned to the reactionchamber for further use.

.In some instances, condensation can best be conducted in the presenceof a high boiling solvent, which is permitted to distill in such amanner as to remove water of reaction. In any event, the speed ofreaction and the character of the polymerized product depends not onlyupon the original reactants themselves, but also on the nature andamount of catalyst employed, on the temperature employed, time ofreaction and speed of water removal, i. e., the effectiveness with whichthe water of reaction is removed from the combining mass. Polymerizationcan be effected without the use of catalysts in the majority ofinstances, but such procedure is generally undesirable, due to the factthat reaction takes a prolonged period of time and usually asignificantly higher temperature. It is noted that in the subsequentexamples the final compositions of matter which are contemplated,particularly for use as demulsifiers, are preferably derived by means ofwater-soluble polymerized hydroxy amines as one of the reactants. Thus,all the subsequent description of polymerized hydroxy amines has beenlimited largely to the type which is watersoluble, and is obviously thepreferred type. How- 1 ever, it must be recognized that polymerizedhydroxy amines, particularly if polymerized for a fairly long period oftime, at a fairly high temperature, and in the presence of an activecatalyst, may result in a polymerization reaction which ends in aproduct that is water-insoluble, or substantially water-insoluble.Obviously, such I water-insoluble material can be obtained more readilyfrom a higher hydroxy amine than from a lower one. In other words,tributanolamine, triliexanolamine, trioctanolamine, etc., would yieldsuch insoluble products much more readily than triethanolamine.

Incidentally, it also must be recognized that the speed of reaction andthe degree of polymerization is effected by the nature of the vessel inwhich the reaction takes place. In the examples cited, it is intendedthat reaction take place in a metal vessel, such as iron. However, inorder to obtain the same degree of polymerization, when conducting thereaction in a glass lined vessel, it is quite likely'that the period ofreaction would have to be increased 150 to 400%.

Suitable hydroxy primary and secondary amines which may be employed toproduce materials of the kind above described includes the following:diethanolamine, monoethanolamine, ethyl ethanolamine, methylethanolamine, propanolamine, dipropanolamine, propyl propanolamine, etc.Other examples include cyclohexanolamine, dicyclohexanolamine,cyclohexyl ethanolamine, cyclohexyl propanolamine, benzyl ethanola- 5mine, benzyl propanolamine, pentanolamine, hexanolamine, octylethanolamine, octadecyl ethanolamine, cyclohexanol ethanolamine, etc.

Similarly, suitable hydroxy tertiary amines which may be employedinclude the following: triethanolamine, diethanolalkylamines, such asdiethanol ethylamine, diethanol propylamine, etc. Other examples includediethanol propylamine, etc. Other examples include diethanolmethylamine, tripropanolamine, dipropanol methylaoxygen of the aldehyde,

mine, cyclohexanol diethanolamine, dicyclohexanol ethanolamine,cyclohexyl diethanolamine, dicyclohexyl ethanolamine, dicyclohexanolethylamine, benzyl diethanolamine, dibenzylethanolamine, benzyldipropanolamine, tripentanolamine, trihexanolamine, ethyl hexylethanolamine, octadecyl'diethanolamine, polyethanolamine, etc.

It is also known that one may have amines of the type:

0111.0 CzH OH (anion cimon 0211.0 ciraon 0111.0 013.011

HN HN C2H40C2H40H CzHaOH such amines may serve as functional equivalentsof the previously described amines.

Attention is directed to the fact that the alkylolamines are obtained insuch a manner that they may be looked upon as being derivatives ofdihydric alcohols, or of the chlorhydrins of the dihydric alcohols. Forexample, the alkylolamines may be prepared as follows:

It is not necessary to point out that the same types of reactidns willproduce secondary or tertiary amines, and that the reaction is notlimited to a combination with ammonia, but may take place with acombination of other primary or secondary amines, such as amylamine,diamylamine, cyclohexylamine, dicyclohexylamine, benzylamine,dibenzylamine, amyl cyclohexylamine, etc. I

This means that in the types of material previously described, there isa wide variety of material, such as mono-glycerylamine, diglycerylamine,monoglyceryl diethylamine, monoglyceryl dipropylamine, diglycerylpropylamirie, triglycerylamine, etc., which are functional equivalentsof the various amines previously described. All that has' been said herein regard to functional equivalents will be perfectly obvious withoutfurther explanation to those skilled in the art. See U. S. Patent No.2,091,704, dated August 31, 1937, to Duncan and McAllister, and also U.S. Patent No. 2,042,621, dated June 2, 1936, to Olin.

Attention is directed to co-pending application for patent Serial No.273,221, filed May 12, 1939, by Melvin De Groote. Said aforementionedapplication describes, among other things, the formation of hydroxydiamines, particularly certain hydroxylated methylene diamines byreactions involving an aldehyde such as formaldehyde, and secondaryamines, as,- for example, diethanolamine. In such reaction the aminohydrogen atoms are removed along with the for instance, the oxygen atomof formaldehyde. The resultant product is tetraethanolmethylene diamine.Such hydroxylated amines, or comparable types, such as polyethylenediamlnes, may be employed. In the polyglycerols, and

amine and a chlorhydrin, such as glycerine chlor-- hydrin, and the like.Examples of hydroxylated amines obtained by the procedure described insaid aforementioned De Groote and Keiser application may be illustratedby the following ex Attention is also directed to the fact that suitableamines include tris(hydroxymethyl) aminomethane, and derivativesthereof, obtained in various manners, for instance, by reaction withchlorhydrins, alkyl chlorides, and the like, particularly ethyleneglycol chlorhydrin, glyceryl monochlorhydrin, etc.

Ponymnmznn Hxpnoxr AMINE Example 1 One percent of caustic soda is addedto commercial triethanolamine and the product heated for approximatelythree hours at 245260 C. The mass is stirred constantly, and anydistillate is condensed and reserved for re-use after an intermediaterunning step. At the end of approxi: mately two and one-half to threeand one-half hours, the molecular weight determination shows that thematerial is largely dimeric.

Pomruxmznn HYDBOXY Ammo Example 2 The same procedure is employed as inthe previous example, except that heating is continued for approximatelyanother hour. In this instance the reaction mass is largely a polymericmaterial with an average molecular weight range indicating the presenceof approximately three to four nitrogen atoms in the polymerized mass.

PoLYMEmzEn Hrmzoxx Amm't Example 3 POLYMEBIZED HYDBOXY AMINE Example 4'Iri-isopropanolamine is substituted for triethanolamine in Examples 1,2 and 3.

POLYMERIZED HYDBOXY AMINE Example 5 Tripentanolamine is substituted fortriethanolamine in Examples 1, 2 and 3.

of two parts of hydroxy amine and one-part of glycerol. One percent ofcaustic soda is added to the mixture and the same procedure employed asindicated in Examples 1, 2 and 3, although there may be some variationnecessary to obtain the proper molecular weight range and surfaceactivity. In any event, molecular weight determinations can be employed,as "well as a foam test of the kind previously described.

POLYMERIZED HYDBOXY AMINE Example 8 Diglycerylamine is substituted fortriethanolamine, in Examples 1, 2 and 3, previously described.

As previously stated, the preferred polymerized hydroxy amines arewater-soluble, but the wateriusoluble type, orsubstantiallywater-insoluble type, of the kind previously referred to, may also beemployed. Furthermore, it must be remembered that the final criterion ofdegree of polymerization, especially in the initial stages, is dependentupon an actual molecular weight determination, rather than based on timeof reaction.

The manufacture of the demulsifler employed in my process involvesnothing more or less than neutralizing the selected petroleum sulfonicacid with a suitable poLvmerized amine so as to neutralize the sulfonichydrogen atom. As a rule, one can employ any suitable indicator, forinstance, methyl orange, litmus, or any other suitable means ofdetermining the neutralization point. For purposes of convenience, Iprefer that the selected petroleum sulfonic acid contain not over 15% ofwater. It is. of course. understood that the conventional procedureemploying double decomposition instead of direct neutralization, can beemployed in the manufacture of my new material or composition of matter.

It may be well to point out that the hydrophile, non-hydrophobepetroleum sulfonic acid or acids of the green acid type varies somewhat.For instance, the molecular weight may vary from the range of 350-500 orthereabouts. Naturally, these petroleum sulfonic acids may carry somepolymerized olefins, free hydrocarbons, or the like, or may even carry abit of naphthenic acids which represent carboxylated, non-sulfonatedpetroleum acids. As previously stated, these materials are well knowncommercial products and are available in the open market, either in theform of the acid itself, or in the form of a salt.

Attention is directed to the fact that some of the polymerizedhydroxyamines herein contemplated produce oil-soluble, water-insolublesalts when employed to neutralize green acids. This is particularly truein regard to those amines which are surface-active per se; i. e., thesolution of the amine in water or in the form of a simple salt, such asthe acetate, shows surface activity, as exemplified by producing,foaming, etc. Whether or not a water-insoluble salt is produced depends,in part, on the molecular weight of the acid; and as has been previouslyindicated, this property may show variation. However, thesurface-active, heat-polymerized hydroxyamines" almost invariablyproduce a water-insoluble product, or at least a product with verylimited water solubility, compared with the sulfonic acid prior toneutralization.

Although it is believed, in view of what has been said previously, thatno further description is required in regard to the manufacture of thenew compounds herein contemplated, and particularly for use ofdemulsifiers, the following examples are added purely by way ofillustration:

Example 1 The same procedure is followed as in Example 1, but instead,the green acids are obtained from Gulf Coast transformer oil extract inthe manner described in U. S. Patent No. 2,203,443, dated June 4, 1940,to Ross and Mitchell.

Example 3 The same procedure is followed as in Example 2, except thatCalifornia 65 Saybolt viscosity Edeleanu extract employed instead ofGulf Coast transformer Edeleanu extract employed in Example 2.

Ea'ample 4 The same procedure is followed as in Example 1, except thatthe product is made from a Gulf Coast naphthene type crude, preferablyof the kind which has little or no low boiling fraction,

i. e., the kind which, on a straight run distillation, gives little orno gasoline.

Example 5 The same procedure is followed as in Examples 1-4, inclusive,except that an amine of the kind exemplified by PolymerizedHydroxyamine, Example 2, is employed instead of the polymerizedhydroxyamine previously referred to.

Example 6 The same procedure is followed as in Example 5 preceding,except that the polymerized hydroxyamine employed is of the kinddescribed in Polymerized Hydroxyamine, Example 3, preceding.

Ezrample 7 The same procedure is followed as in Example 5 preceding,except that the polymerized hydroxyamine employed is of the kinddescribed in Polymerized Hydroxyamine, Example 6, preceding.

Example 10 The same procedure is followed as in Example 5 preceding,except that the polymerized hydroxyamine employed is of the kinddescribed in Polymerized Hydroxyamine, Example '7, preceding.

Ea'ample 11 The same procedure is followed as in Example 5 preceding,except that the polymerized hydroxyamine employed is of the kinddescribed in Polymerized Hydroxyamine, Example 8, preceding.

Conventional demulsifying agents employed in the treatment of oil fieldemulsions are used as such, or after dilution with any suitable solvent,such as water, petroleum hydrocarbons, such as gasoline, kerosene, stoveoil, a coal tar product, such as benzene, toluene, xylene, tar acidoihcresol, anthracene oil, etc. Alcohols, particularly aliphaticalcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol,propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., maybe employed as diluents. Miscellaneous solvents, such as pine oil,carbon tetrachloride, sulfur dioxide extract obtained in the refining ofpetroleum, etc., may be employed as diluents. Similarly, the material ormaterials employed as the demulsifying agent of my process may beadmixed with one or more of the solvents customarily used in connectionwith conventional demulsifying agents. Moreover, said material ormaterials may be used alone, or in admixture with other suitable wellknown classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in awater-soluble form, or in an oil-soluble form, or in a form exhibitingboth oil and water solubility. Sometimes they may be used in a formwhich exhibits relatively limited oil solubility. However, since suchreagents are sometimes used in a ratio of 1 to 10,000, or 1 to 20,000,or even 1 to 30,000, such an apparent insolubility in oil and water isnot signiflcant, because said reagents undoubtedly have solubilitywithin the concentration employed. This same fact is true in regard tothe material or materials employed as the demulsifying agent of myprocess.

I desire to point out that the superiority of the reagent ordemulsifying agent contemplated in my process is based upon its abilityto treat certain emulsions more advantageously and at a somewhat lowercost than is possible with other available demulsifiers, or conventionalmixtures thereof. It is believed that the particular demulsifying agentor treating agent herein described will find comparatively limitedapplication, so far as the majority of oil field emulsions areconcerned; but I have found that such a demulsifying agent hascommercial value, as it will economically break or resolve oil fieldemulsions in a number of cases which cannot treated as easily or at solow a cost with the demulsiiying agents heretofore available.

In practising my process, a treating agent or demulsifying agent of thekind above described is brought into contact with or caused to act uponthe emulsion to be treated, in any of the various ways, or by any of thevarious apparatus now -generally used to resolve or break petroleumemulsions with a chemical reagent, the above procedure being used eitheralone or in combination with other demulsifying procedure, such as theelectrical dehydration process.

The demulsifier herein contemplated may be employed in connection withwhat is commonly known as down-the-hole procedure, i. e., bringing the'demulsifier in contact with the fluids of the well at the bottom of thewell, or at some point prior to their emergence. This particular type ofapplication is decidedly feasible when the demulsifier is used inconnection with acidification or calcareous oil-bearing strata,especially if suspended in or dissolved in the acid employed foracidification.

Having thus described my invention, what I 018g? as new and desire tosecure by Letters Paten s:

1. A process for resolving petroleum emulsions of the water-in-oil type,characterized by sub- J'ecting the emulsion to the action of ademulsifier comprising a. chemical compound consisting of the salt of abasic amine; said amine salt being obtained from a watersoluble,non-hydrophobe petroleum sulfonic acid of the green acid type and aheat-polymerized basic hydroxyamine.

2. A process for resolving petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsiflercomprising a chemical compound consisting of the salt of abasic amine;said amine salt being obtained from a water-soluble, non-hydrophobepetroleum sulfonic acid of the green acid type and a non-acylatedheat-polymerized basic hydroxyamine.

3. A process for resolving petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsiflercomprising a chemical compound consisting of the salt of a basic amine;said amine salt being obtained from a water-soluble, non-hydrophobepetroleum sulfonic acid of a green acid type and a non-acylatedheat-polymerized basic hydroxyamine free from an ether radical derivedfrom a monohydric alcohol.

4. A process for resolving petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsifiercomprising a chemical compound consisting of the salt of a basic amine;said amine salt being obtained from a water-soluble, non-hydrophobepetroleum sulfonic acid of the green acid ,type and a non-acylatedheat-polymerized basic hydroxyamine free from an ether radical derivedfrom an alcohol. 7

5. A process for resolving petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsifiercomprising a chemical compound consisting of the salt of a basic amine;said amine salt being obtained from a water-soluble, non-hydrophobepetroleum sulfonic acid of the green acid type and a water-soluble.non-acylated heat-polymerized basic hydroxyamine free from an etherradical derived from an alcohol.

6. A process for resolving petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsiflercomprising a chemical compound consisting of the salt of a basic amine;said amine salt being obtained from a water-soluble, non-hydrophobepetroleumsulfonic acid of the green acid type and a water-solublenon-acylated ,heat-polymerized basic hydroxyamine of the dimeric type,free from an ether linkage derived from an alcohol. I

7. A process for resolving petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsifiercomprising a chemical compound consisting of the salt of a basic amine;said amine salt being obtained from a water-soluble, non-hydrophobepetroleum sulfonic acid 01' the green acid type and a water-solublenon-acylated heat-polymerized basic hydroxyamine of the polymeric type,free from an ether linkage derived from an alcohol.

, EDWIN E. CLAYTOR.

